Yellow acridinium dye.



NITED STATES PATENT OFFICEQ FRITZ ULLMANN, OF EURTH, GERMANY, ASSIGNORTO THE ACTIEN- GESELLSCHAFT FUR ANILIN FABRIKATION, OF SAME PLACE.

YELLOW ACRIDINIUM DYE.

QPECIFICATION forming part of Letters Patent No. 643,569, dated February13, 1900.

Application filed September 7, 1899. Serial No. 729,769. (Specimens) Toall whom it may concern.-

Be it known that I, Fnfirz ULLMANN, of Fiirth, in the Kingdom ofBavaria, German Empire, have invented new and useful Improvements inAcridinium Dyestuffs; and I do hereby declare that the following is afull, clear, and exact description of the invention, which will enableothers skilled in the art to which it appertains to make and use thesame.

'My invention relates to the production of new coloring-matters from theso-called acridin dyestuffs.

As is well known, the dyestufis belonging to the acridin series arecharacterized by the acridin group contained in them, as shown in thefollowing formula for the typical acridin:

iii

- by substituting for hydrogen in the OH group connecting the two nucleia phenyl or substituted phenyl group. The acridin dyestuffs themselvesare derivatives of these acridin bases containing in the hydrocarbonnuclei one or several amido groups, the hydrogen of which may again besubstituted partly or totally by other radicles. All acridin d yestuifsare further characterized by the fact that their salts are easilydecomposed by sodium car-v bonate, the free color base beingprecipitated. Owing to this behavior the shades obtained by means ofacridin dyestuffs are not fast to alkalies.

It is now my invention to have found that acridin dyestuffs may beconverted into new valuable coloring-matters which are fast to alkaliesby the addition of alkyl to the nitrogen of the acridin radicle. Thetrivalent nitrogen by this treatment becomes pentavalent and productsare formed which in analogy to the ammonium compounds maybe termedacridinium compounds. Their constitution is represented by the followingtypical formula:

in which Alk represents an alkyl and R an acid radicle.

The acridinium dyestuffs are essentially distinguished from the acridindyestufis from which they are derived by the following properties: Thesalts of the acridinium dyestuffs are not decomposed by means of alkalicarbonates. In consequence thereof the tints obtained with theacridinium dycstuifs are fast to alkalies. The acridinium dyestuffsfurther yield considerably clearer and more brilliant tints and theirshades are more red or more orange than those obtained by thecorresponding acridin dyes.

As regards the process of the alkylation of the acridins I have furtherfound that dimethyl sulfate (or diethyl sulfate) is a most suitableagent for effecting the transformation of the acridin group into theacridinium group. If, for instance, the typical acridin is treated withdimethyl sulfate the reaction proceeds as shown in the followingequation:

li ll 0 OIL, SO

OOH

the methylsulfuric salt of the acridiniu m base being formed.

In order to indicate how my invention can practically be carried out, Igive in the following example a description of the manufacture of anacridinium dyestuif from the amidotolunaphthacridin described in EnglishPatent No. 16,474, 1898.

Two parts, by weight,of amidotolunaphthacridiu (English Patent No.16,474, 1898) are dissolved in the heat in twenty parts of nitrobenzene,and to the boiling solution is added onepartofdimethylsulfate.Thenewaeridinium compound separates at once in the form of the puremethyl-sulfuric salt. The dyestuit thus obtained forms abrown-red powdereasily soluble in water with red color. The aqueous solution is notaltered by addition of ammonia or sodium carbonate; buton addition ofcaustic-soda lye the free color base is separated in shape of aredprecipitate soluble in other with red color and green fluorescence.

The dyestulf dyes tannin-mordanted cotton clear orange-yellow shades.

In quite the same manner as shown in the above typical example and withpractically the same result other acridin dyes may be converted into thecorresponding acridinium derivatives by means of dimethyl sulfate. Thus,for instance, my new process may be applied to coloringma-tters such asacridinyellow, acridin-orange, benzoflavine, and the like. The resultingcoloring-matters closely resemble the dyestuff described in the aboveexample.

Having now described my invention and in what manner the same can beperformed, what I claim as new is- 1. A new dye derived from the acridinseries, which can be obtained as a methyl-sulf uric salt by treating anacridin dyestuif with dym ethyl sulfate, this new dye being the salt ofan amido derivative of the typical acridinium:

H ll

no Alk.

in which formula Alk represents an alkyl and in which the two benzenenuclei may one or both be replaced by homologous groups or by thenaphthalene nucleus, the salt of the new acridinium color-base being notdecomposed by sodium carbonate or ammonia, the free base only beingprecipitated by means of caustic alkalies the salt forming a yellow orred powder readily soluble in water with yellow color and bitter taste,the new dyestuff dyeing tannin-mordanted cotton orange-yellow shades.

2. As a specific dye the dyestulf obtained as a methyl-sulfuric salt bytreating amidotolunaphthacridin with dimethyl sulfate, themethyl-sulfuric salt formed being represented by the formula:

oon,

forming a brown-red powder easily soluble in water with yellow. color,the solution being not altered by sodium carbonate or ammonia, but beingprecipitated by means of caustic alkalies, the free color bases thusseparating in form of a red precipitate soluble in ether with red colorand green fluorescence, the new dyestuif dyeing tannin mordanted cottonclear orange-yellow shades.

In witness whereof I have hereunto signed my name, this 24th day ofAugust, 1899, in the presence of two subscribing witnesses.

FRITZ ULLMANN.

\Vitnesses:

FRITZ ULLMANN, OSCAR BooK.

